THE THERMOCHEMISTRY OF THE MERCAPTOMETHYL (CH2SH+) AND THIOMETHOXY (CH3S+) CATIONS - A COMPARISON OF G2 THEORY AND EXPERIMENT

被引：54

作者：

NOBES, RH ^{[1
]}

RADOM, L ^{[1
]}

机构：

[1] AUSTRALIAN NATL UNIV,RES SCH CHEM,CANBERRA,ACT 2601,AUSTRALIA

来源：

CHEMICAL PHYSICS LETTERS | 1992年 / 189卷 / 06期

关键词：

D O I：

10.1016/0009-2614(92)85249-A

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Ab initio calculations at the G2 level of theory have been used to predict an energy difference between the mercaptomethyl (CH2SH+, 1) and thiomethoxy (CH3S+, 2) cations of 131 kJ mol-1 in favour of 1. Reasons for the discrepancy with a recent experimental estimate of 163-172 kJ mol-1 are explored. Calculated heats of formation (DELTA-H(f0); DELTA-H(f298)) for CH2S (121; 117 kJ mol-1), CH3S (129; 122 kJ mol-1), CH3S+ (1015; 1008 kJ mol-1) and CH2SH+ (884; 876 kJ mol-1) are presented.

引用

页码：554 / 559

页数：6

共 31 条

[1] IONS [CH3S]+ [C2H5S]+ AND [CH3O]+ FORMED BY ELECTRON-IMPACT
AMOS, D
GILLIS, RG
OCCOLOWI.JL
PISANI, JF
[J]. ORGANIC MASS SPECTROMETRY, 1969, 2 (02): : 209 - &
[2] [Anonymous], 1986, AB INITIO MOL ORBITA
[3] ENERGETICS AND STRUCTURES OF ORGANOSULFUR IONS - CH3SSCH3+, CH3SS+, C2H5S+, AND CH2SH+
BUTLER, JJ
BAER, T
EVANS, SA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (11) : 3451 - 3455
[4] ENERGIES OF CH2OH, CH3O, AND RELATED-COMPOUNDS
CURTISS, LA
KOCK, LD
POPLE, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (06) : 4040 - 4043
[5] GAUSSIAN-2 THEORY FOR MOLECULAR-ENERGIES OF 1ST-ROW AND 2ND-ROW COMPOUNDS
CURTISS, LA
RAGHAVACHARI, K
TRUCKS, GW
POPLE, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (11) : 7221 - 7230
[6] COLLISIONAL ACTIVATION AND METASTABLE ION CHARACTERISTICS .65. COLLISIONAL ACTIVATION AND THEORETICAL STUDIES OF GASEOUS CSH3+ IONS
DILL, JD
MCLAFFERTY, FW
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (22) : 6526 - 6531
[7] COLLISIONAL ACTIVATION AND METASTABLE ION CHARACTERISTICS .61. STRUCTURES AND RELATIVE ENERGIES OF GASEOUS CSH3+IONS
DILL, JD
MCLAFFERTY, FW
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (09) : 2907 - 2908
[8] SOME C-S, H-S AND S-S BOND STRENGTHS BY THE ELECTRON IMPACT METHOD
FRANKLIN, JL
LUMPKIN, HE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1952, 74 (04) : 1023 - 1026
[9] FRISCH MJ, 1990, GAUSSIAN 90
[10] ELECTRON IMPACT STUDIES OF SOME SULPHIDES AND DISULPHIDES
GOWENLOCK, BG
MAJER, JR
KAY, J
[J]. TRANSACTIONS OF THE FARADAY SOCIETY, 1963, 59 (491): : 2463 - &

← 1 2 3 4 →